Process of making alpha-oxythionaphthenes.



1 UNITED sTATEs PATENT OFFICE.

BENNO HOMOLKA, OF FRANKFORT-ON-THE MAIN, AND RICHARD WELDE, OFHOOHST-ON- THE-MAIN, GERMANY, ASSIGNORS TO FARBWERKE VORM. MEISTER-LUOIUS dz B'RUNING,

OF HOCHST-O'N TI-IE-MAIN, GERMANY.

A CORPORATION 01* GER-MANY.

PROCESS OF MAKING ALPHA-OXY THIONAPHTI IENE S.

To all whom it may concern:

Be it known that We, BENXO HoMoLKA, Ph. 1)., and RICHARD VVELDE,Pl1. 1chemists, citizens of the Empire of Germany, and

residing at Frankfort on the Main and I-Iochst-on-the-Uain. Germany,respectively, have invented certain new and useful Improvements inMaking Alpha-Oxythionaphthenes, of Which the following is a specificasmaybe obtained, if methylthiophenol-o-car boxylic acid,

COOH (1) .H.{

SCH3 its salts or esters be heated With alkaline condensing agents. Ifthe substitution products of methylthiophenal-ortho-carboxylic acid be 0used, substituted alpha-oxythicaaphthenes are obtained. As alkalinecondensing agents are specially to be considered caustic alkalies andalkaline earths, alkali and alkaline earth metals by themselves or inform of alloys or amalgams, alkaline alcoholates and dialkaline salts ofcyanamid. The al haoxy-thionaphthenes thus obtained'yiel by the actionof oxidizing agents valuable dyestuffs.

Example 1.. A mixture of 10 parts by Weight of methylthiophenol ocarboxylic acid methyl ester, 8 parts by Weight of sodium or potassiumalcoholate and 30-50 parts by Weight of an approximately molecularmixture of potassium and sodium hydroxid is made to melt. At about 1500' occurs the formation of alpha oxythionaphthene which is complete atabout 200 G. Then cold'the mass is dissolved in Water and thealplia-oxythionaphthe'ne is isolated after adding an excess of carbonicor mineral acid by filtration or distilling over by means of steam. Itmay be transformed into a red vat dyestuif by means of oxygen of the airor artificial oxidizing agents.

Specification of Letters Patent.

Application filed February 5, 1907.

Patented July 21, 1908. Serial No. 355.872.

In the above example may be substituted for alkali alcoholate thedisodium-cyanamid under otherwise like or similar conditions.

Example II. A thorough mixture of 10 parts by Weight of sodiummethylthiophenolo-carboxylate, 10 parts by Weight of finely pulverizedquick-lime and 30-50 parts of.a molecular mixture of caustic potash andcaustic soda is made to melt. The formation of alpha-thionaphtheneoccurs at about 200 (1; it is, however, preferable to some- ,what raisethe temperature and to maintain it till no furthermethylthiophenol-O-carboxylic acid can be traced in a test portiondissolved in Water and acidified with hydrochloric acid. Thealpha-oxythionaphthene further Worked up and isolated is similar to thatdescribed in Example I. v

Example III. Into 100 parts by weight of an approximately molecularmixture of caustic potash and caustic soda heated to about 200 C areintroduced While stirring 20 parts by Weight of an alloy of sodium (10percent.) and lead and 10 parts by weight of the sodium salt ofIndtamethyl-tl1iocresol ortho-carboxyiic acid, keeping the-fusion atthis temperature, till no further meta-methyh thiocresol orthocarboxylic acid can be traced. When cold the mass is extracted WithWater and the solution is converted in the usual manner intomethyl-alpha-oxythionaphthene. When oxidized it yields a vat dyestuffdyeing W001 and cotton in red tints.

Example IV. One part by weight of sodiummethylthiophenol-p-ethoxy-ocarboxylate is introduced into about 10 partsby Weight of a molecular mixture of caustic potash and caustic sodaheated to 180 0.; the temperature is raised to about 200-210 and themelt maintained at it While stirring, till any unchanged parent materialis no longer traced. When cold the mass is dissolved in Water and thealpha-oxythionaphthene thus obtained is separated in .the usual manner.It may be transformed by means of oxidizing agents into a dyestuflcyeing. in the vat Wool and cotton in violet tints.

Having now described our invention, What as our invention, We havesigned our names weTilairlrll is: d t 1 in presence of two subscribingWitnesses. c erein describe process 0' me (in T T Jalpha-0xytl1ionephthenes, which consists lI l 5 heating the salts ofmethylthioph enol-ortho carboxylic acids with alkaline condensingWitnesses:

agents. JEAN GRUND,

In testimony, that We claim the foregoing CARL GRUND.

